Phosphorescent Materials

ABSTRACT

Phosphorescent materials and devices with high device efficiency, stability, and processibility.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application60/905,758 filed Mar. 8, 2007, which is incorporated herein by referencein its entirety.

BACKGROUND OF THE INVENTION

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a jointuniversity-corporation research agreement: Princeton University, TheUniversity of Southern California, and the Universal DisplayCorporation. The agreement was in effect on and before the date theclaimed invention was made, and the claimed invention was made as aresult of activities undertaken within the scope of the agreement.

Electronic display currently is a primary means for rapid delivery ofinformation. Television sets, computer monitors, instrument displaypanels, calculators, printers, wireless phones, handheld computers, etc.aptly illustrate the speed, versatility, and interactivity that ischaracteristic of this medium. Of the known electronic displaytechnologies, organic light emitting devices (OLEDs) are of considerableinterest for their potential role in the development of full color,flat-panel display systems that may render obsolete the bulky cathoderay tubes still currently used in many television sets and computermonitors.

Generally, OLEDs are comprised of several organic layers in which atleast one of the layers can be made to electroluminesce by applying avoltage across the device (see, e.g., Tang, et al., Appl. Phys. Lett.1987, 51, 913 and Burroughes, et al., Nature, 1990, 347, 359). When avoltage is applied across a device, the cathode effectively reduces theadjacent organic layers (i.e., injects electrons), and the anodeeffectively oxidizes the adjacent organic layers (i.e., injects holes).Holes and electrons migrate across the device toward their respectiveoppositely charged electrodes. When a hole and electron meet on the samemolecule, recombination is said to occur, and an exciton is formed.Recombination of the hole and electron in luminescent compounds isaccompanied by radiative emission, thereby producingelectroluminescence.

Depending on the spin states of the hole and electron, the excitonresulting from hole and electron recombination can have either a tripletor singlet spin state. Luminescence from a singlet exciton results influorescence, whereas luminescence from a triplet exciton results inphosphorescence. Statistically, for organic materials typically used inOLEDs, one quarter of the excitons are singlets, and the remainingthree-quarters are triplets (see, e.g., Baldo, et al., Phys. Rev. B,1999, 60, 14422). Until the discovery that there were certainphosphorescent materials that could be used to fabricate practicalelectro-phosphorescent OLEDs (U.S. Pat. No. 6,303,238) and,subsequently, demonstration that such electro-phosphorescent OLEDs couldhave a theoretical quantum efficiency of up to 100% (i.e., harvestingall of both triplets and singlets), the most efficient OLEDs weretypically based on materials that fluoresced. Fluorescent materialsluminesce with a maximum theoretical quantum efficiency of only 25%(where quantum efficiency of an OLED refers to the efficiency with whichholes and electrons recombine to produce luminescence), since thetriplet to ground state transition of phosphorescent emission isformally a spin forbidden process. Electro-phosphorescent OLEDs have nowbeen shown to have superior overall device efficiencies as compared withelectro-fluorescent OLEDs (see, e.g., Baldo, et al., Nature, 1998, 395,151 and Baldo, et al., Appl. Phys. Lett. 1999, 75(3), 4).

Due to strong spin-orbit coupling that leads to singlet-triplet statemixing, heavy metal complexes often display efficient phosphorescentemission from such triplets at room temperature. Accordingly, OLEDscomprising such complexes have been shown to have internal quantumefficiencies of more than 75% (Adachi, et al., Appl. Phys. Lett., 2000,77, 904). Certain organometallic iridium complexes have been reported ashaving intense phosphorescence (Lamansky, et al., Inorganic Chemistry,2001, 40, 1704), and efficient OLEDs emitting in the green to redspectrum have been prepared with these complexes (Lamansky, et al., J.Am. Chem. Soc., 2001, 123, 4304). Red-emitting devices containingiridium complexes have been prepared according to U.S. Pat. No.6,821,645. Phosphorescent heavy metal organometallic complexes and theirrespective devices have also been the subject of International PatentApplication Publications WO 00/57676, WO 00/70655, and WO 01/41512; U.S.Publications 2006/0202194 and 2006/0204785; and U.S. Pat. Nos.7,001,536; 6,911,271; 6,939,624; and 6,835,469.

Despite the recent discoveries of efficient heavy metal phosphors andthe resulting advancements in OLED technology, there remains a need foreven greater efficiency in devices. Fabrication of brighter devices thatuse less power and have longer lifetimes will contribute to thedevelopment of new display technologies and help realize the currentgoals toward full color electronic display on flat surfaces. Thephosphorescent organometallic compounds, and the devices comprisingthem, described herein, help fulfill these and other needs.

SUMMARY OF THE INVENTION

In one embodiment, an iridium compound has a formula:

wherein n is 1, 2 or 3; each of R₁, R₂, and R₃ is independently ahydrogen, or a mono-, di-, tri-, tetra-, or penta-substitution of alkylor aryl; at least one of R₁, R₂, and R₃ is a branched alkyl containingat least 4 carbon atoms, and wherein the branching occurs at a positionfurther than the benzylic position; and X—Y is an ancillary ligand. Thebranched alkyl can be an isobutyl group. The X—Y ligand can be acac.Specific exemplary compounds are also provided.

In another embodiment, a compound includes a ligand having the formula:

each of R₁, R₂, and R₃ is independently a hydrogen, or a mono-, di-,tri-, tetra-, or penta-substitution of alkyl or aryl; at least one ofR₁, R₂, and R₃ is a branched alkyl containing at least 4 carbon atoms,and wherein the branching occurs at a position further than the benzylicposition. The ligand can be coordinated to a metal having an atomicnumber greater than 40, e.g., Ir.

In yet another embodiment, specific compounds are provided, e.g.,Compounds 1-24.

In yet another embodiment, an organic light emitting device comprises ananode, a cathode, and an emissive organic layer disposed between theanode and the cathode. The organic emissive layer comprises one or moreof the compounds provided. The organic emissive layer can furthercomprise, e.g., Compound C or BAlq.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows an organic light emitting device having separate electrontransport, hole transport, and emissive layers, as well as other layers.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

FIG. 3 shows examples of iridium compounds.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, and a cathode 160. Cathode 160 is acompound cathode having a first conductive layer 162 and a secondconductive layer 164. Device 100 may be fabricated by depositing thelayers described, in order. The properties and functions of thesevarious layers, as well as example materials, are described in moredetail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporatedby reference.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe invention may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional LEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Numerous Ir(2-phenylquinoline) and Ir(1-phenylisoquinoline) typephosphorescent materials have been synthesized, and OLEDs incorporatingthem as the dopant emitters have been fabricated. The devices mayadvantageously exhibit high current efficiency, high stability, narrowemission, high processibility (such as high solubility and lowevaporation temperature), high luminous efficiency, and/or high luminousefficiency: quantum efficiency ratio (LE:EQE).

Using the base structure of Ir(3-Meppy)₃, different alkyl and fluorosubstitution patters were studied to establish a structure-propertyrelationship with respect to material processibility (evaporationtemperature, evaporation stability, solubility, etc.) and devicecharacteristics of Ir(2-phenylquinoline) and Ir(1-phenylisoquinoline)type phosphorescent materials and their PHOLEDs. Alkyl and fluorosubstitutions are particular important because they offer a wide rangeof tenability in terms of evaporation temperature, solubility, energylevels, device efficiency, etc. Moreover, they are stable as functionalgroups chemically and in device operation when applied appropriately.

In one embodiment, an iridium compound has the formula (also illustratedin FIG. 3):

-   -   wherein n is 1, 2 or 3;    -   each of R₁, R₂, and R₃ is independently a hydrogen, or a mono-,        di-, tri-, tetra-, or penta-substitution of alkyl or aryl;    -   at least one of R₁, R₂, and R₃ is a branched alkyl containing at        least 4 carbon atoms, and wherein the branching occurs at a        position further than the benzylic position; and    -   X—Y is an ancillary ligand.

Together, X and Y represent a bidentate ligand. Numerous bidentateligands are known to those skilled in the art and many suitable examplesare provided in Cotton and Wilkinson, Advanced Inorganic Chemistry,Fourth Ed., John Wiley & Sons, New York, 1980. In some embodiments,bidentate ligands are monoanionic. Suitable bidentate ligands include,but are not limited to, acetylacetonate (acac), picolinate (pic),hexafluoroacetylacetonate, salicylidene, 8-hydroxyquinolinate; aminoacids, salicylaldehydes, and iminoacetonates. In one embodiment, X—Y isacac. Bidentate ligands also include biaryl compounds. In someembodiments, the biaryl compounds coordinate to the metal atom through acarbon atom and a nitrogen atom. As used herein, the term “biaryl”refers to compounds comprising two aryl groups covalently joined by asingle bond. The aryl groups of a biaryl compound can be aryl orheteroaryl, including both monocyclic or poly-cyclic aryl and heteroarylgroups. Exemplary biaryl groups include, but are not limited to,biphenyl, bipyridyl, phenylpyridyl, and derivatives thereof. Biarylcompounds can serve as bidentate ligands in metal coordinationcomplexes, for instance, by coordinating though one atom in each of thetwo aryl groups. The coordinating atoms can be carbon or a heteroatom.Further suitable bidentate ligands include, but are not limited to,2-(1-naphthyl)benzoxazole, 2-phenylbenzoxazole, 2-phenylbenzothiazole,coumarin, thienylpyridine, phenylpyridine, benzothienylpyridine,3-methoxy-2-phenylpyridine, thienylpyridine, tolylpyridine,phenylimines, vinylpyridines, arylquinolines, pyridylnaphthalenes,pyridylpyrroles, pyridylimidazoles, phenylindoles, and derivativesthereof. Suitable bidentate ligands also include those provided by U.S.Pat. Nos. 7,001,536; 6,911,271; 6,939,624; and 6,835,469.

In another embodiment, X and Y can each be a monodentate ligand, thatis, any ligand capable of coordinating to a metal atom through one atom.Numerous monodentate ligands are well known in the art, and manysuitable examples are provided in Cotton and Wilkinson, supra. In someembodiments, monodentate ligands can include F, Cl, Br, I, CO, CN,CN(R⁴), SR⁴, SCN, OCN, P(R⁴)₃, P(OR⁴)₃, N(R⁴)₃, NO, N₃, or anitrogen-containing heterocycle optionally substituted by one or moresubstituents X. Each R⁴ is independently H, C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, C₁-C₂₀ heteroalkyl, C₃-C₄₀ aryl, C₃-C₄₀heteroaryl. R⁴ is optionally substituted by one or more substituents X,wherein each X is independently H, F, Cl, Br, I, R⁵, OR⁵, N(R⁵)₂,P(R⁵)₂, P(OR⁵)₂, POR⁵, PO₂R⁵, PO₃R⁵, SR⁵, Si(R⁵)₃, B(R⁵)₂,B(OR⁵)₂C(O)R⁵, C(O)OR⁵, C(O)N(R⁵)₂, CN, NO₂, SO₂, SOR⁵, SO₂R⁵, or SO₃R⁵.Each R⁵ is independently H, C₁-C₂₀ alkyl, C₁-C₂₀ perhaloalkyl, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, C₁-C₂₀ heteroalkyl, C₃-C₄₀ aryl, or C₃-C₄₀heteroaryl. The phrase “nitrogen-containing heterocycle” as used hereinrefers to any heterocyclic group containing at least one nitrogen atom.Nitrogen-containing heterocycles can be saturated or unsaturated andinclude, but are not limited to, pyridine, imidazole, pyrrolidine,piperidine, morpholine, pyrimidine, pyrazine, pyridazine, pyrrole,1,3,4-triazole, tetrazole, oxazole, thiazole, and derivatives thereof.In further embodiments, one of X and Y is a neutral monodentate ligand,and the other of X and Y is monoanionic, i.e., X and Y have a combinedcharge of (−1). For example, X can be chloro, and Y can be pyridyl.

Some of the compounds provided comprise at least one bidentatephenylquinolinato (pq) ligand. The term phenylquinolinato, or pq, asused herein refers to both substituted and non-substituted ligands, andthe number (n) of coordinated pq ligands can be 1, 2, or 3. In someembodiments, compounds comprise m-1 pq ligands (wherein m is the formalcharge of the metal) or, in some embodiments, two pq ligands.Phenylquinolinato ligands can be substituted with substituents R₁, R₂,and R₃ as defined above. Any combination of substituents is suitable.Adjacently-positioned substituents can, together, comprise a 4- to7-member cyclic group that is fused to the ligand. For example, thepairs R₁ and R₂ or R₂ and R₃ can comprise a fused cyclic group. Thephrase “fused cyclic group” refers to a cyclic group that shares one ormore bonds with a further cyclic group. The pq ligands can have anynumber of fused cyclic group substituents. Any feasible combination offused cyclic groups and the remaining of R₁, R₂, and R₃ not involved ina fused cyclic group is contemplated.

As used herein, the term “alkyl” includes linear, branched, and cyclicalkyl groups. In some embodiments, alkyl groups are C₁-C₂₀ alkyl groups.Exemplary alkyl groups include, but are not limited to, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, cyclohexyl, and norbornyl. Inone embodiment, the compound includes a branched aryl, wherein thebranching occurs at a position further than the benzylic position. Thebenzylic position is the carbon attached directly to the aryl ring.Thus, in this embodiment, the alkyl chain projects linearly from thearyl ring for at least two carbons until branching begins. The branchedalkyl can be, e.g., an isobutyl group.

As used herein, the term “heteroalkyl” refers to alkyl groups includingone or more heteroatoms such as O, S, or N. Heteroalkyl groups can alsocomprise unsaturations. Exemplary heteroalkyl groups include, but arenot limited to, pyrrolidinyl, piperidinyl, and morpholinyl. The term“perhaloalkyl” refers to alkyl groups substituted by halogen. Exemplaryperhaloalkyl group include, but are not limited to, trifluoromethyl,trichloromethyl, and pentafluoroethyl. “Alkenyl” groups refer to alkylgroups having one or more double bonds, and “alkynyl” groups refer toalkyl groups having one or more triple bonds. “Aryl” groups can be anymono- or polycyclic aromatic group, and “heteroaryl” refers to an arylgroup including one or more heteroatoms such as 0, S, or N. Aryl groupscan have about 3 to about 40 carbon atoms and include, but are notlimited to, phenyl, 4-methylphenyl, naphthyl, anthracenyl, andphenanthryl. Heteroaryl groups include, but are not limited to, pyridyl,indolyl, benzothiophene, and quinolinyl. “Amino” groups as used hereininclude amino, alkylamino, dialkylamino, arylamino, and diarylaminogroups. Exemplary amino groups include, but are not limited to, NH₂,methylamino, dimethylamino, phenylamino, and diphenylamino. “Halo”groups are halogens including, e.g., fluoro, chloro, bromo, and iodo.

Specific examples of compounds of formula I or II include:

In another embodiment, a compound including a ligand has the formula:

-   -   wherein each of R₁, R₂, and R₃ is independently a hydrogen, or a        mono-, di-, tri-, tetra-, or penta-substitution of alkyl or        aryl;    -   at least one of R₁, R₂, and R₃ is a branched alkyl containing at        least 4 carbon atoms, and    -   wherein the branching occurs at a position further than the        benzylic position.

In one embodiment, the ligand is coordinated to a metal having an atomicnumber greater than 40. The metal can be any metal atom, includingsecond and third row transition metals, lanthanides, actinides, maingroup metals, alkali metals, and alkaline earth metals. Heavy metals mayprovide thermal stability and superior phosphorescent properties. Secondrow transition metals include any of Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, andCd, and third row transition metals include any of La, Hf, Ta, W, Re,Os, Ir, Pt, Au, and Hg. Main group metals include, e.g., In, Sn, Sb, Tl,Pb, Bi, and Po. In some embodiments, M is Ir, Os, Pt, Pb, Re, or Ru. Inother embodiments, the metal atom is Ir. The metal atom M can have anyformal charge designated as m. In some embodiments, the formal charge ispositive such as 1+, 2+, 3+, 4+, 5+, 6+, 7+, or 8+. In one embodiment,formal charge is greater than 1+. In another embodiment, formal chargeis greater than 2+. In yet another embodiment, formal charge can be 3+.

In another embodiment, a compound is selected from the group consistingof:

Some of the compounds provided can be photoluminescent. In someembodiments, the compounds are efficient phosphors having, for example,a significant portion of luminescence arising from phosphorescentemission. In some embodiments, the emission can be red or reddish. Colorof emission can be estimated from the photoluminescence spectrum. Aluminescence maximum of about 550 to about 700 nm can indicate red orreddish emission. A maximum at lower wavelengths can indicate green orblue emission. Additionally, the color of emission can be described bycolor index coordinates x and y (Commision Internationale de L'Eclairage(CIE) 1931 standard 2-degree observer; see, e.g., Shoustikov, et al.,IEEE Journal of Selected Topics in Quantum Electronics, 1998, 4, 3;Dartnall, et al., Proceedings of the Royal Society of London B, 1983,220, 115; Gupta, et al., Journal of Photochemistry, 1985, 30, 173;Colorimetry, 2.sup.nd ed., Publication CIE 15.2-1986 (ISBN3-900-734-00-3)). For example, a compound emitting in the reds can havecoordinates of about 0.5 to about 0.8 for x and about 0.2 to about 0.5for y.

Some of the compounds provided may advantageously emit a more saturatedhue, particular red. In other words, the compounds may emit a color thatis closer to the pure spectral colors falling along the outside curve ofthe chromaticity diagram, i.e., colors that are produced by a singlewavelength of light. The compounds may exhibit a narrower emission thanother comparative compounds. Alternatively, the compounds may exhibit anemission profile that is closer to an industry standard hue fordisplays.

Processes for preparing compounds are also provided. Phenylquinolinatoligands (L) having desired substitutions can be made using the generalprocedure of coupling phenyl boronic acid having desired substitutionwith chloroquinoline (e.g., 2-chloroquinoline, 3-chloroisoquinoline, or2-chloroisoquinoline) also having desired substitution. Couplingprocedures can be, for example, conducted under Suzuki conditions in thepresence of palladium(II) (see, e.g., Miyaura, et al., Chem. Rev. 1995,2457). The quinoline (or isoquinoline) and boronic acid startingmaterials can be obtained from commercial sources or synthesized bymethods known in the art. For example, 3-chloroisoquinoline can be madeaccording to the procedures described in Haworth, R. D., et al., J Chem.Soc., 1948, 777.

Phenylquinoline ligands (L) having desired substitution can becoordinated to a metal atom by, for example, contacting the ligands witha metal halide complex. Metal halide complexes include compoundscomprising at least one metal coordinated to one or more halide ligands.Metal halide complexes can be of the Formula M(Q)_(q) where Q is ahalide ligand and q is the number of halide ligands. For example, q canbe about 2 to about 6. For the preparation of iridium-containingcompounds, the metal halide complex can be IrCl₃. This and other metalhalide complexes are well known in the art and commercially available.Under sufficient time and conditions, the contacting can result in theformation of a metal-containing intermediate, having mixed coordinationof halide and phenylquinoline ligands L. In some embodiments, the metalatom of the intermediate can coordinate to at least one L. In otherembodiments, the metal atom of the intermediate can coordinate two L. Infurther embodiments, the intermediate can be polynuclear comprising, forexample, more than one metal atom and bridging halide ligands. When themetal halide complex is IrCl₃, the metal-containing intermediate can bean iridium dimer complex having, for example, the structureL₂Ir(μ-Cl)₂IrL₂. Any remaining halide ligands of the intermediate,including bridging halides, can be replaced by ligand substitution withone or more ancillary ligands, such as represented by X and Y in FormulaI or II. For example, 2,4-pentanedione in the presence of base canreplace coordinated halide ligands in the metal-containing intermediateto give an acetylacetonato complex. Syntheses of exemplary compounds areprovided in the Examples.

Some of the compounds provided can be used as emitters in organic lightemitting devices. Accordingly, the compounds can be present in anemissive layer (i.e., a layer from which light is primarily emitted) ofa such device. The emissive layer can be, for example, a layerconsisting essentially of one or more of the compounds provided. Some ofthe compounds provided can also be present as dopants. For example, anemissive layer can comprise host material doped with one or more of thecompounds provided. The host material can comprise any compound,including organic and organometallic compounds, suitable in an emissivelayer in an OLED. Exemplary organic host materials include, but are notlimited to, BCP (bathocuproine or2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), CBP(4,4′-N,N′-dicarbazole biphenyl), OXD7(1,3-bis(N,N-t-butylphenyl)-1,3,4-oxadiazole), TAZ(3-phenyl-4-(1′-naphthyl)-5-phenyl-1,2,4-triazole), NPD(4,4′-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl), CuPc (copperphthalocyanine), Alq₃ (aluminum tris(8-hydroxyquinolate)), and BAlq((1,1′-biphenyl)-4-olato)bis(2-methyl-8-quinolinolato N1,O8)aluminum).Other materials that can be included in an emissive layer in addition tothe emissive compounds include Irppy(tris(2-phenylpyridinato-N,C2′)iridium(III)), Flrpic(bis(2-(4,6-difluorophenyl)pyridinato-N,C2′)iridium(III)(picolinate)),and other metal complexes such as those described in U.S. Pat. No.7,001,536; U.S. Pat. Nos. 6,911,271; and 6,939,624. As dopants, some ofthe compounds provided can be present in the emissive layer, such as inhost material, in amounts of about 1 to about 20 wt %, about 5 to about15 wt %, about 5 to about 10 wt %, or other similar ranges.

In one embodiment, specific combinations of dopants and hosts areprovided. For example, the organic emissive layer can comprise BAlq orCompound C.

In one embodiment, the organic emissive layer comprises Compound 1 andCompound C. In another embodiment, the organic emissive layer comprisesCompound 9 and Compound C. In yet another embodiment, the organicemissive layer comprises Compound 22 and BAlq. In still anotherembodiment, the organic emissive layer comprises Compound 24 and BAlq.

Accordingly, in another embodiment, a composition comprises one or moreof the compounds provided. In some embodiments, compositions comprise atleast one of the compounds provided and a further compound suitable foruse in an OLED. For example, further compounds can include any of thehost materials mentioned above. Additionally, further compounds caninclude other emitters or metal complexes, such as Flrpic, Irppy, andother complexes mentioned above.

Devices comprising at least one of the compounds provided may havesuperior properties as compared with known devices. For example, highexternal quantum and luminous efficiencies can be achieved in thepresent devices. Device lifetimes are also generally better than, or atleast comparable to, some of the most stable fluorescent devicesreported.

Table 1 provides data for devices using exemplary compounds as well asdevices using Comparative Examples 1 and 2:

TABLE 1 70° C. Lifetime comparison Tsubl at EML At 10 mA/cm² T_(80%) at40 mA/cm² (hr) (L₀)²(T80%) 0.24 Å/ dopant λ FWHM V LE EQE L₀ at 70° C.Dopant s (° C.) % max (nm) CIE (V) (cd/A) (%) LE:EQE (cd/m²) RT 70° C.(×10⁹) Comp. 206 12 622 94 0.65 0.35 8.1 14.3 14 1.01 4817  991 60 1.39Ex. 1 Comp. 229 9 630 84 0.68 0.32 9.1 11.1 15 0.72 3808 1200 180 2.61Ex. 2 1 192 12 622 66 0.67 0.33 8.8 18.3 17.7 1.03 6382 n.m. 73 2.97 2220 12 634 82 0.68 0.32 8.9 9.6 13.5 0.71 3308 n.m. 127 1.39 3 200 12632 80 0.68 0.32 8.8 10.8 15.6 0.69 3784 n.m. 145 2.08 4 186 12 630 820.68 0.32 9.49 11.07 16 0.69 3852 n.m. 132 1.96 5 206 12 626 82 0.660.33 8.8 14.6 16.1 0.91 5175 n.m. 55 1.47 6 207 12 628 86 0.67 0.32 911.2 15.3 0.73 4007 n.m. 127 2.04 7 202 12 626 83 0.66 0.34 8.6 14.3 141.02 4877 n.m. 127 3.02 8 177-185 12 636 70 0.69 0.31 8.6 9.8 14.6 0.673390 n.m. 38 0.44 9 163-172 12 618 61 0.66 0.34 9.2 23.5 18.8 1.25 7992n.m. 60 3.83 13 211 12 618 78 0.65 0.35 9.1 20.1 17.2 1.17 6865 n.m. 522.45 14 212 12 632 80 0.67 0.33 9.6 7.9 10.1 0.78 2810 n.m. 32 0.25 15217 12 622 66 0.665 0.333 8.9 18.6 17.5 1.06 6411 n.m. 40 1.64 16 186 12618 65 0.658 0.340 9.8 22.4 18.7 1.20 7593 n.m. 10.6 0.61 20 210 12 62079 0.655 0.347 8.7 16.8 15.4 1.09 6026 n.m. 80 2.91 22 210 12 637 660.693 0.304 9.5 9.8 17.5 0.56 3277 n.m. 80 0.86 24 218 12 635 66 0.691,0.306 8.9 11.5 19.0 0.61 3894 n.m. 90 1.36 n.m. = not measured

As shown in Table 1, several exemplary compounds demonstrated efficiencyand lifetime that was is better than, or at least comparable to, thecomparative examples. For example, the LE and EQE of Compound 1 are 18.3cd/A and 17.7%, respectively, at CIE of (0.67, 0.33). The LE:EQE ratiois 1.03, which is significantly higher than that of Comparative Example2 (LE:EQE=0.72), which is only slightly more red (0.68, 0.32). The 70°C. lifetime comparison shows that Compound 1 is more stable thanComparative Example 2. Compound 1 is the best deep red emitter to datein the industry.

Some exemplary compounds also have high LE:EQE ratios compared toComparative Examples 1 with similar CIE coordinates (0.65-0.66,0.34-0.35) due to the narrow emission profile of the exemplarycompounds. For example, Compound 9 has a deeper red CIE than ComparativeExample 1, yet the LE:EQE ratio of Compound 9 is 1.25, which issignificantly higher than that of Comparative Example 1 (1.01).

Table 2 shows data for devices using exemplary compounds as well asdevices using Comparative Examples.

TABLE 2 At 10 mA/cm² T_(80%) at 40 mA/cm² Tsubl at 0.24 Å/s λ FWHM LEEQE L₀ (hr) Dopant (° C.) max (nm) CIE V (V) (cd/A) (%) LE:EQE (cd/m²)RT 70° C. Comp. Ex. 3 200-210 602 78 0.61 8.5 27.1 16.6 1.63 9370 200n.m. 0.38 Comp. Ex. 4 237 618 78 0.65 8 9.8 8.8 1.11 3622 530 n.m. 0.34 1 192 622 66 0.67 8.8 18.3 17.7 1.03 6382 n.m. 73 0.33 Comp. Ex. 5 229632 84 0.68 8.8 10.6 15.2 0.70 3757 n.m. 240  0.32 22 210 637 66 0.6939.5 9.8 17.5 0.56 3277 n.m. 80 0.304

As shown by Table 2, Compound 1 has lower sublimation temperature,higher efficiency, and narrower emission compared with ComparativeExamples 3 and 4. Similarly, Compound 22 has a lower sublimationtemperature, higher efficiency, and narrower emission compared withComparative Example 5.

Compounds having branched alkyl substitution may be particularadvantageous. Branched alkyl substitutions on red compounds seem toimprove lineshape, efficiency, and lifetime. Table 3 shows data fordevices using exemplary compounds, including those having branched alkylsubstitutions, as well as devices using Comparative Examples.

TABLE 3 At 10 mA/cm² T_(80%) at 40 mA/cm² Tsubl at 0.24 Å/s λ FWHM LEEQE L₀ (hr) Dopant (° C.) max (nm) CIE V (V) (cd/A) (%) LE:EQE (cd/m²)RT 70° C. Comp. Ex. 6 190 618 64 0.66 8.7 20 16.8 1.19 7014 n.m. 31 0.34 9 198 618 61 0.66 9.2 23.5 18.8 1.25 7992 n.m. 60 0.34 16 186 618 650.658 9.8 22.4 18.7 1.20 7593 n.m. 10.6 0.340 20 210 620 79 0.655 8.716.8 15.4 1.09 6026 n.m. 80 0.347 Comp. Ex. 7 237 618 78 0.65 8 9.8 8.81.11 3622 530 n.m. 0.34

As shown by Table 3, isobutyl substitutions on either quinoline orphenyl ring resulted in higher efficiency and longer lifetime. Comparedto methyl and n-propyl substitution on the 7 position of quinoline, theisobutyl substitution maintained the emission maximum. However, thespectrum is narrower than methyl or n-propyl substitution. The fullwidth of half maxima (FWHM) decreased to 61 nm, which resulted in ahigher ratio of current efficiency to external quantum efficiency. Inaddition, isobutyl substitution shows much longer lifetime than methyland n-propyl substitution.

When the methyl group was replaced by isobutyl group on the phenyl ring(see Compound 20 and Comparative Example 7), the evaporation temperaturedecreased by 27 degrees. The emission slightly shifted to a moresaturated red color. Again, the external quantum efficiency increasedfrom 8.8% to 15.4%.

In some embodiments, e.g., those comprising Ir, the device emits red.Red devices can have electroluminescence maxima of about 550 to about700 nm. Similarly, color index coordinates (CIE) for red devices can beabout 0.5 to about 0.8 for x and about 0.2 to about 0.5 for y. In someembodiments, devices, e.g., red devices, can have external quantumefficiencies greater than about 4%, 5%, 6%, 7%, 8%, 10%, 12%, or higherat a brightness greater than about 10, 100, 1000 cd/m², or more.

Typical devices are structured so that one or more layers are sandwichedbetween a hole injecting anode layer and an electron injecting cathodelayer. The sandwiched layers have two sides, one facing the anode andthe other facing the cathode. Layers are generally deposited on asubstrate, such as glass, on which either the anode layer or the cathodelayer may reside. In some embodiments, the anode layer is in contactwith the substrate. In some embodiments, for example when the substratecomprises a conductive or semi-conductive material, an insulatingmaterial can be inserted between the electrode layer and the substrate.Typical substrate materials may be rigid, flexible, transparent, oropaque, and include, but are not limited to, glass, polymers, quartz,and sapphire.

In some embodiments, devices comprise further layers in addition to alayer comprising at least one of compounds provided (e.g., an emissivelayer). For example, in addition to the electrodes, devices can includeany one or more of hole blocking layers, electron blocking layers,exciton blocking layers, hole transporting layers, electron transportinglayers, hole injection layers, and electron injection layers. Anodes cancomprise an oxide material such as indium-tin oxide (ITO), Zn—In—SnO₂,SbO₂, or the like, and cathodes can comprises a metal layer such as Mg,Mg:Ag, or LiF:Al. Among other materials, the hole transporting layer(HTL) can comprise triaryl amines or metal complexes such as thosedescribed in U.S. Pat. No. 7,261,954. Similarly, the electrontransporting layer (ETL) can comprise, for example, aluminumtris(8-hydroxyquinolate) (Alq₃) or other suitable materials.Additionally, a hole injection layer can comprise, for example,4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (MTDATA),polymeric material such as poly(3,4-ethylenedioxythiophene) (PEDOT),metal complex such as copper phthalocyanine (CuPc), or other suitablematerials. Hole blocking, electron blocking, and exciton blocking layerscan comprise, for example, BCP, BAlq, and other suitable materials suchas Flrpic or other metal complexes described in U.S. Pat. No. 7,261,954.Some of the compounds provided can also be included in any of the abovementioned layers.

Light emitting devices can be fabricated by a variety of well-knowntechniques. Small molecule layers, including those comprised of neutralmetal complexes, can be prepared by vacuum deposition, organic vaporphase deposition (OVPD), such as disclosed in U.S. Pat. No. 6,337,102,or solution processing such as spin coating. Polymeric films can bedeposited by spin coating and chemical vapor deposition (CVD). Layers ofcharged compounds, such as salts of charged metal complexes, can beprepared by solution methods such a spin coating or by an OVPD methodsuch as disclosed in U.S. Pat. No. 5,554,220. Layer depositiongenerally, although not necessarily, proceeds in the direction of theanode to the cathode, and the anode typically rests on a substrate.Devices and techniques for their fabrication are described throughoutthe literature, e.g., U.S. Pat. Nos. 5,703,436; 5,986,401; 6,013,982;6,097,147; and 6,166,489. For devices from which light emission isdirected substantially out of the bottom of the device (i.e., substrateside), a transparent anode material such as ITO may be used as thebottom electron. Since the top electrode of such a device does not needto be transparent, such a top electrode, which is typically a cathode,may be comprised of a thick and reflective metal layer having a highelectrical conductivity. In contrast, for transparent or top-emittingdevices, a transparent cathode may be used such as disclosed in U.S.Pat. Nos. 5,703,436 and 5,707,745. Top-emitting devices may have anopaque and/or reflective substrate, such that light is producedsubstantially out of the top of the device. Devices can also be fullytransparent, emitting from both top and bottom.

Transparent cathodes, such as those used in top-emitting devicespreferably have optical transmission characteristics such that thedevice has an optical transmission of at least about 50%, although loweroptical transmissions can be used. In some embodiments, devices includetransparent cathodes having optical characteristics that permit thedevices to have optical transmissions of at least about 70%, 85%, ormore. Transparent cathodes, such as those described in U.S. Pat. Nos.5,703,436 and 5,707,745, typically comprise a thin layer of metal suchas Mg:Ag with a thickness, for example, that is less than about 100 Å.The Mg:Ag layer can be coated with a transparent,electrically-conductive, sputter-deposited ITO layer. Such cathodes areoften referred to as compound cathodes or as TOLED (transparent-OLED)cathodes. The thickness of the Mg:Ag and ITO layers in compound cathodesmay each be adjusted to produce the desired combination of both highoptical transmission and high electrical conductivity, for example, anelectrical conductivity as reflected by an overall cathode resistivityof about 30 to 100 ohms per square. However, even though such arelatively low resistivity can be acceptable for certain types ofapplications, such a resistivity can still be somewhat too high forpassive matrix array OLED pixels in which the current that powers eachpixel needs to be conducted across the entire array through the narrowstrips of the compound cathode.

Light emitting devices can be used in a pixel for an electronic display.Virtually any type of electronic display can incorporate the devices.Displays include, but are not limited to, computer monitors,televisions, personal digital assistants, printers, instrument panels,and bill boards. In particular, the devices can be used in flat-paneldisplays and heads-up displays.

The following examples are illustrative only and are not intended to belimiting. Those skilled in the art will recognize, or be able toascertain through routine experimentation, numerous equivalents to thespecific substances and procedures described herein. Such equivalentsare considered to be within the scope of the claimed invention. Allreferences named herein are expressly and entirely incorporated byreference.

EXAMPLES

In the exemplary syntheses described herein, the following reagents areabbreviated as follows:

-   DME 1,2-dimethoxyethane-   Pd₂(dba)₃ Tris(dibenzylideneacetone)dipalladium-   Pd(OAc)₂ Palladium acetate-   Pd(PPh₃)₄ Tetrakis(triphenylphosphine)palladium-   Ph₃P Triphenylphosphine-   RuCl₂(PPh₃)₃ Dichlorotris(triphenylphosphine)ruthenium (III)-   THF Tetrahydrofuran

Synthesis of Compound 1

Step 1

To a 500 mL round bottle flask, 9.0 g (˜54.4 mmol) of 2-chloroquinoline,9.2 g (59.8 mmol) of 3,5-dimethylphenylboronic acid, 1.8 g (1.5 mmol) ofPd(PPh₃)₄, 22.4 g (163 mmol) of K₂CO₃, 150 mL of DME, and 150 mL ofwater were charged. The reaction mixture was heated to reflux undernitrogen overnight. The reaction mixture was cooled, and the organicextracts were purified by a silica gel column chromatography (10% ethylacetate in hexane as eluent). The material obtained was further purifiedby vacuum distillation (Kugelrohr) at 185° C. to yield 12.2 g (95%yield) of product as a colorless liquid.

Step 2

46 g (197.4 mmol) of the product from Step 1, 536 mL of2-methoxyethanol, and 178 mL of water were charged in a 1000 mLthree-neck flask. The reaction mixture was bubbled with nitrogen for 45min with stirring. Then 32 g (86.2 mmol) of IrCl₃.H₂O was added intothis mixture and heated to reflux (100-105° C.) under nitrogen for 17hrs. The reaction mixture was cooled and filtered. The black-gray solidwas washed with methanol (4×50 mL) followed by hexane (3×300 mL). 36.5 gof the dimer was obtained after drying in a vacuum oven. The dimer wasused for the next step without further purification.

Step 3

36 g of the dimer (26 mmol), 120 g of 2,4-pentanedione (˜1200 mmol), 66g (622 mmol) of sodium carbonate, and about 500 mL of 2-methoxyethanolwere added in a 1000 mL round bottle flask. The reaction mixture wasvigorously stirred at room temperature for 24 hrs. The reaction mixturewas then suction filtered and washed with methanol (3×250 mL) followedby hexane (4×300 mL). The solid was collected and stirred in ˜1000 mL ofa solvent mixture (900 mL of methylene chloride and 100 mL oftriethylamine) for ˜10 min. Then the mixture was gravity filtered with aWhatman Quality 1 Circle filter paper. ˜20 g of red final product (52%yield) was obtained after evaporating the solvent in the filtrate (99.5%pure with non-acidic HPLC column).

Synthesis of Compound 2

Step 1

4.5 g (25 mmol) of 2-chloro-3-methyl-quinoline, 5.0 g (30 mmol) of3-isopropylphenylboronic acid, 17.3 g (75 mmol) of potassium phosphatemonohydrate, 0.4 g (1.0 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, 100 mL of toluene, and25 mL of water were added to a 250 mL three-neck flask. The system waspurged with nitrogen for 30 min before 0.23 g (0.25 mmol) of Pd₂(dba)₃was added to the mixture. The reaction mixture was then heated to refluxfor 3 hrs. After cooled to room temperature, the layers were separated.The aqueous layer was extracted with ethyl acetate. The organic layerswere combined, washed with water, and dried over magnesium sulfate.After evaporating the solvent, the residue was purified by columnchromatography using hexanes and ethyl acetate as the eluent. Thechromatographed product was further purified by distillation to yield6.0 g (92% yield) of product (99.7% pure).

Step 2

5.4 g (20.7 mmol) of the product from Step 1 and 3.2 g (9.0 mmol) ofiridium chloride were mixed in 90 mL of 2-ethoxyethanol and 30 mL ofwater. The mixture was heated to reflux overnight. The solvent wasevaporated. 60 mL of 2-ethoxyethanol was added, and the mixture washeated to reflux for another 40 hrs. After cooled to room temperature,the solid was collected by filtration. 3.2 g of the dimer was obtained.The dimer was used for the next step without further purification.

Step 3

3.2 g of the dimer, 10 mL of 2,4-pentanedione, and 2.5 g of sodiumcarbonate were added to 50 mL of 1,2-dichloroethane and heated to refluxovernight. After cooled to room temperature, the mixture was filtered.The filtrate was concentrated and run through a triethylamine treatedsilica gel column. The final compound was sublimed twice, yielding 0.63g of 98.7% pure product.

Synthesis of Compound 3

Step 1

A mixture of 1-chloroisoquinoline (5.0 g, 30.56 mmol),4-isopropylphenylboronic acid (5.5 g, 33.62 mmol), Pd(OAc)₂ (0.34 g,1.53 mmol), Ph₃P (1.60 g, 6.11 mmol), and K₂CO₃ (10.98 g, 79.46 mmol) in25 mL water and 25 mL of 1,2-dimethoxyethane was stirred and purged withnitrogen for 30 min. The mixture was heated to reflux overnight undernitrogen. The reaction mixture was cooled to room temperature, and waterwas added, followed by ethyl acetate. The layers were separated, and theaqueous layer was extracted with ethyl acetate. The organic extractswere washed with water, brine, dried over magnesium sulfate, filtered,and evaporated. The residue was purified by column chromatographyeluting with 0, 5, and 10% ethyl acetate/hexanes. The chromatographedproduct was purified by distillation using a Kugelrohr at 180° C. toyield 5.56 g (74% yield) of the product as a clear oil.

Step 2

A mixture of the ligand from Step 1 (5.56 g, 22.48 mmol), iridiumchloride (3.78 g, 10.2 mmol), 2-ethoxyethanol (45 mL), and 15 mL ofwater was refluxed overnight under nitrogen. The mixture was cooled toroom temperature, and the solid was filtered, washed with methanol,dried, and used without further purification.

Step 3

A mixture of the dimer, 2,4-pentanedione (10.5 mL, 102 mmol), and K₂CO₃(4.23 g, 30.6 mmol) in 75 mL of 2-ethoxyethanol was refluxed overnightunder nitrogen. The reaction is was cooled to room temperature andmethanol was added. A red solid was filtered off and washed withmethanol. The solid was purified by column chromatography. The columnwas treated with 20% triethylamine/hexanes prior to purification, theneluted with 20 and 50% dichloromethane/hexanes after loading the solidto the column. 4.2 g (53% yield) of a red solid was obtained as theproduct, which was further purified by recrystallization fromacetonitrile followed by sublimation at 250° C.

Synthesis of Compound 4

Step 1

1-chloroisoquinoline (2.95 g, 18.00 mmol) was dissolved in 25 mL of DMEand 25 mL of water. 4-sec-butylphenylboronic acid (3.36 g, 18.90 mmol),Ph₃P (0.94 g, 3.60 mmol), and K₂CO₃ (7.46 g, 54.01 mmol) were added, andthe mixture was stirred and purged with nitrogen for 30 min. Pd(OAc)₂(0.20 g, 0.90 mmol) was added, and the mixture was refluxed overnight.The product was extracted with ethyl acetate, washed with water, anddried over sodium sulfate. Chromatography (0-20% ethyl acetate/hexanes)yielded a light yellow oil. Further purification by Kugelrohrdistillation at 185° C. gave 2.52 g the product as a clear oil.

Step 2

The ligand from Step 1 (2.52 g, 9.64 mmol) was combined with iridiumchloride (1.62 g, 4.38 mmol) in 40 mL of 3:1 ethoxyethanol:water andrefluxed for 24 hrs. The mixture was cooled to room temperature, and thesolid was filtered, washed with methanol, dried, and used withoutfurther purification.

Step 3

The dimer was suspended in 25 mL of ethoxyethanol. 2,4-pentanedione(4.51 mL, 43.83 mmol) and K₂CO₃ (1.82 g, 13.15 mmol) were added, and thereaction was refluxed overnight. After cooling the mixture was pouredinto a large excess of stirring methanol. A red precipitate was filteredand purified by column chromatography (column pretreated with 20%triethylamine/hexanes, run with 0-20% dichloromethane/hexanes) to givered solids, which were further purified by recrystallization fromacetonitrile followed by sublimation at 200° C., yielding 0.41 g ofproduct (99.1% pure).

Synthesis of Compound 5

Step 1

2-Amino-5-fluorobenzoic acid (10.0 g, 64.46 mmol) was dissolved in 50 mLof THF and cooled to 0° C. 1.0 M of lithium aluminum hydride in THF(79.93 mL, 79.93 mmol) was added dropwise. The mixture was allowed towarm to room temperature and stirred for 6 hrs. The reaction was placedin an ice bath and 3 mL of water was added dropwise. 50 mL of 1.0 N NaOHwas added dropwise and stirred for 15 min. 50 mL of water was added andstirred for 15 min. The mixture was extracted with ethyl acetate, washedwith water, and concentrated to a volume of about 100 mL. This was thenpoured into a large excess of stirring hexanes. The precipitate thatformed was filtered, washed with hexanes, and dried under vacuum toyield 6.71 g of off-white solids as the product.

Step 2

The product from Step 1 (6.71 g, 47.56 mmol) was combined with3-methylacetophenone (11.28 g, 84.13 mmol), RuCl₂(PPh₃)₃ (0.05 g, 0.05mmol), and potassium hydroxide (0.83 g, 0.02 mmol) in 70 mL of tolueneand refluxed overnight using a Dean-Stark trap to remove water. Thereaction was cooled to room temperature, and a small amount of Celitewas added to the mixture, which was then filtered through a silica gelplug. The filtrate was concentrated. Purification was achieved bychromatography (5% ethyl acetate/hexanes) and vacuum distillation at200° C. to yield 6.59 g of yellow solids as the product.

Step 3

The ligand from Step 2 (6.59 g, 26.22 mmol) was combined with iridiumchloride (4.41 g, 11.92 mmol) in 80 mL of a 3:1 methoxyethanol:watersolution. The mixture was purged with nitrogen for 20 min and refluxedovernight. The dark red precipitate that formed was filtered off, washedwith methanol and hexanes, and used for the next step without furtherpurification.

Step 4

The dimer (17.39 g, 11.92 mmol) was suspended in 50 mL of ethoxyethanol.2,4-pentanedione (12.28 mL, 119.20 mmol), and sodium carbonate (3.79 g,35.76 mmol) were added, and the reaction was stirred overnight at roomtemperature. The mixture was poured into a large excess of stirringmethanol. A red precipitate formed and was filtered off. Thisprecipitate was dissolved in dichloromethane, poured into stirringmethanol, and filtered to give a red solid. This procedure was repeated.This solid was dried under vacuum to yield 4.40 g of red solid as theproduct, which was further purified by two sublimations yielding 3.21 g(99.9% pure).

Synthesis of Compound 6

Step 1

5.9 g (0.075 mol) of pyridine and 5 g (0.025 mol)4-isopropylphenylethylamine hydrochloride were added to a three-neckround-bottom flask with 25 mL of dichloromethane as the solvent. Thesolution was cooled in an ice bath, and 3.2 mL (0.027 mol) of benzoylchloride was added slowly via a syringe. The solution was warmed to roomtemperature and stirred for 12 hrs. Dichloromethane was added, and theorganic phase was washed with water, 5% HCl solution, 5% NaOH solution,and dried over MgSO₄. The solvent was evaporated resulting in 7.5 g ofcrude product, which was used without further purification.

Step 2

N-(4-p-isopropylphenylethyl)benzamide (7.5 g), 25 g phosphorouspentoxide, and 25 mL of phosphorous oxychloride in 80 mL of xylenes wererefluxed for 3 hrs. After cooling, the solvent was decanted, and ice wasslowly added to the solid. The water-residue mixture was made weaklyalkaline with 50% NaOH, and the product was extracted with toluene. Theorganic layer was washed with water and dried over MgSO₄. The solventwas evaporated resulting in 6.2 g of crude product, which was usedwithout further purification.

Step 3

6.2 g of 7-isopropyl-1-phenyl-3,4-dihydroisoquinoline and 1 g of 5% Pd/C(-10% by weight) were added to a round-bottom flask with 100 mL ofxylenes. The solution was refluxed for 24 hrs, and the formation of theproduct was monitored by TLC. The xylenes solvent was removed, and theproduct was purified by column chromatography with ethylacetate/hexanes. The pure fractions were collected, and the solvent wasremoved. The product was then distilled in a Kugelrohr apparatus at 185°C. affording 1.8 g (0.0073 mol) of pure product. The overall yield ofligand formation was ˜15%.

Step 4

A mixture of 1.8 g of the 1-phenyl-7-isopropylisoquinoline ligand(0.0073 mol) and 1.2 g of IrCl₃ (0.0036 mol) in 25 mL of 2-ethoxyethanoland 5 mL of water was refluxed for 18 hrs. Upon cooling, the red soliddimer was filtered and washed with 300 mL of methanol resulting in 1.3 g(25% yield) of crude product.

Step 5

1.3 g of the dimer (0.0009 mol), 2 mL of 2,4-pentandione, and 1 g ofsodium carbonate were added to a flask with 25 mL of 2-ethoxyethanol.The solution was refluxed for 12 hrs. After cooling, the product was runthrough a Celite plug with dichloromethane as the solvent. The solventwas removed, and the product was precipitated from 2-ethoxyethanol byadding water. The compound was dissolved in dichloromethane, dried withMgSO₄, filtered, and the solvent was evaporated. The compound waspurified by column chromatography using dichloromethane and hexane asthe eluent. The pure fractions were collected, and the solvent wasremoved. The compound was purified by a second column treated withtriethylamine using dichloromethane solvent resulting in 0.55 g ofproduct. The material was sublimed under vacuum at 210° C. resulting in0.35 (50% yield) of the product.

Synthesis of Compound 7

Step 1

2-Amino-4-fluorobenzoic acid (10.0 g, 64.46 mmol) was dissolved in 50 mLof THF and cooled to 0° C. 1.0 M of lithium aluminum hydride in THF(79.93 mL, 79.93 mmol) was added dropwise. The mixture was allowed towarm to room temperature and stirred for about 6 hrs. The reaction wasplaced in an ice bath, and 3.0 mL of water was added dropwise. 50 mL of1N NaOH was added dropwise and stirred for 15 min. 50 mL of water wasadded and stirred for 15 min. The mixture was extracted with ethylacetate, washed with water, and concentrated to a volume of about 100mL. This was then poured into a large excess of stirring hexanes. Theprecipitate that formed was filtered, washed with hexanes, and driedunder vacuum to yield 6.71 g of off-white solids.

Step 2

The product from Step 1 (6.71 g, 47.5 mmol) was combined with3-methylacetophenone (11.28 g, 84.13 mmol), RuCl₂(PPh₃)₃ (0.05 g, 0.048mmol) and potassium hydroxide (0.83 g, 0.015 mmol) in 70 mL of tolueneand refluxed overnight using a Dean-Stark trap to remove water. Thereaction was cooled to room temperature, and a small amount of Celitewas added to the mixture, which was then filtered through a silica gelplug and concentrated. Purification was achieved by chromatography (5%ethyl acetate/hexanes) followed by vacuum distillation at 200° C. toyield 6.59 g of yellow solids.

Step 3

The ligand from Step 2 (6.59 g, 26.22 mmol) was combined with iridiumchloride (4.41 g, 11.92 mmol) in 80 mL of a 3:1 methoxyethanol:watersolution. The mixture was purged with nitrogen for 20 min and refluxedovernight. The dark red precipitate that formed was filtered off, washedwith methanol and hexanes, and used for the next step.

Step 4

The dimer (17.39 g, 11.92 mmol) was suspended in 50 mL of ethoxyethanol.2,4-pentanedione (12.28 mL, 119.20 mmol) and sodium carbonate (3.79 g,35.76 mmol) were added, and the reaction was stirred overnight at roomtemperature. The reaction was poured into a large excess of stirringmethanol. The red precipitate formed was filtered off, dissolved indichloromethane, poured into stirring methanol, and filtered to give ared solid. This procedure was repeated. This solid was dried undervacuum to yield 4.40 g of red solid which was further purified by twosublimations, yielding 3.21 g of red solids (99.8% pure).

Synthesis of Compound 8

Step 1

2-Amino-6-fluorobenzoic acid (10.0 g, 64.46 mmol) was dissolved in 50 mLof THF and cooled to 0° C. 1.0 M lithium aluminum hydride in THF (79.93mL, 79.93 mmol) was added dropwise. The mixture was allowed to warm toroom temperature and stirred for about 60 hrs. The reaction was placedin an ice bath, and 3 mL of water was added dropwise. 50 mL of 1N NaOHwas added dropwise and stirred for 15 min. 50 mL of water was added andstirred for 15 min. The mixture was extracted with ethyl acetate, washedwith water, and concentrated to a volume of about 100 mL. This was thenpoured into a large excess of stirring hexanes. The precipitate formedwas filtered, washed with hexanes and dried under vacuum to yield 6.71 gof off-white solids.

Step 2

The product from Step 1 (6.71 g, 47.56 mmol) was combined with3,5-dimethylacetophenone (11.28 g, 76.09 mmol), RuCl₂(PPh₃)₃ (0.05 g,0.048 mmol) and potassium hydroxide (0.83 g, 0.015 mmol) in 70 mL oftoluene and refluxed overnight using a Dean-Stark trap to remove water.The reaction was cooled to room temperature, and a small amount ofCelite was added to the mixture, which was then filtered through asilica gel plug and concentrated. Purification was achieved bychromatography (5% ethyl acetate/hexanes) and two Kugelrohrdistillations at 200° C. to yield 6.59 g of yellow solids.

Step 3

The ligand from Step 3 (6.59 g, 26.22 mmol) was combined with iridiumchloride (4.41 g, 11.92 mmol) in 80 mL of a 3:1 methoxyethanol:watersolution. The mixture was purged with nitrogen for 20 min and refluxedovernight. The black precipitate formed was filtered off, washed withmethanol and hexanes, and used for the next step.

Step 4

The dimer (17.39 g, 11.92 mmol) was suspended in 50 mL of ethoxyethanol.2,4-pentanedione (12.28 mL, 119.20 mmol) and sodium carbonate (3.79 g,35.76 mmol) were added, and the reaction was stirred overnight at roomtemperature. The reaction was poured into a large excess of stirringmethanol. The red precipitate that formed was filtered off, dissolved indichloromethane, poured into stirring methanol and filtered to give ared solid. This procedure was repeated. This solid was dried undervacuum to yield 4.40 g red solid, which was further purified by twosublimations, yielding 3.21 g red solids (99.0% pure).

Synthesis of Compound 9

Step 1

42.8 g of 2-amino-4-chlorobenzoic acid was dissolved in 200 mL of THFand cooled with an ice-water bath. To the solution was added 11.76 g oflithium aluminum hydride chips. The resulting mixture was stirred atroom temperature for 8 hrs. 12 g of water was added followed by 12 g of15% NaOH. 36 g of water was then added. The slurry was stirred at roomtemperature for 30 min. The slurry was filtered. The solid was washedwith ethyl acetate. The liquid was combined, and the solvent wasevaporated. The crude material was used for next step withoutpurification.

Step 2

6.6 g of (2-amino-4-chlorophenyl)methanol, 10 g of1-(3,5-dimethylphenyl)ethanone, 0.1 g of RuCl₂(PPh₃)₃, and 2.4 gpotassium hydroxide in 100 mL of toluene were refluxed for 10 hrs. Waterwas collected from the reaction using a Dean-Stark trap. After cooled toroom temperature, the mixture was filtered through a silica gel plug.The product was further purified with column chromatography using 2%ethyl acetate in hexanes as solvent to yield 9 g product. The productwas further recrystallized from isopropanol. 5 g of product wasobtained.

Step 3

3.75 g of 7-chloro-2-(3,5-dimethylphenyl)quinoline, 2.8 g ofisobutylboronic acid, 0.26 g of Pd₂(dba)₃, 0.47 g of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, and 16 g of potassiumphosphate monohydrate were mixed in 100 mL of toluene. The system wasdegassed for 20 min and heated to reflux overnight. After cooled to roomtemperature, the crude product was purified by column chromatographyusing 2% ethyl acetate in hexanes as solvent. 3.6 g of product wasobtained.

Step 4

3.2 g of 2-(3,5-dimethylphenyl)-7-isobutylquinoline and 1.8 g of iridiumchloride were mixed in 45 mL of methoxyethanol and 15 mL of water. Afterdegassed for 10 min, the mixture was heated to reflux overnight. Aftercooled to room temperature, the precipitate was filtered and washed withmethanol and hexanes. The dimer was then dried under vacuum and used fornext step without further purification. 2.2 g of the dimer was obtainedafter vacuum drying.

Step 5

2.2 g of the dimer, 1.4 g of 2,4-pentanedione, and 0.83 g of sodiumcarbonate were mixed in 35 mL of 2-ethoxyethanol and stirred at roomtemperature for 24 hrs. The precipitate was filtered and washed withmethanol. The solid was redissolved in dichloromethane. Afterevaporating the solvent, the solid was sublimed under high vacuum at210° C. twice to obtain 1 g of final product.

Synthesis of Compound 10

Step 1

A mixture 1-chloroisoquinoline (5.0 g, 30.56 mmol), 4-ethylphenylboronicacid (5.04 g, 33.62 mmol), Ph₃P (1.60 g, 6.11 mmol), K₂CO₃ (10.98 g,79.46 mmol), 25 mL of dimethoxyethane, and 25 mL of water was purgedwith nitrogen for 30 min. Pd(OAc)₂ was then added (0.34 g, 1.53 mmol),and the mixture was heated to reflux overnight under nitrogen. Thecooled solution was diluted with water and ethyl acetate. The layerswere separated, and the aqueous layer extracted with ethyl acetate. Theorganic layers were dried over magnesium sulfate, filtered, andevaporated to a residue. The residue was purified by columnchromatography eluting with 0 to 20% ethyl acetate/hexanes. Thechromatographed product was purified by Kugelrohr distillation to yield5.74 g (81% yield) of product.

Step 2

A mixture of 1-(4-ethylphenyl)isoquinoline (5.74 g, 24.60 mmol), iridiumchloride (4.14 g, 11.18 mmol), 45 mL of 2-ethoxyethanol, and 15 mL ofwater was refluxed for 2 days under nitrogen. The cooled mixture wasfiltered, washed with water and methanol, and allowed to air dry.

Step 3

The dimer was mixed with 2,4-pentanedione (12.1 mL, 111.8 mmol), K₂CO₃(4.64 g, 33.54 mmol), and 2-ethoxyethanol (75 mL) and heated to refluxunder nitrogen. The cooled mixture was filtered, and the red solid wasrinsed with methanol. The solid was purified by column chromatography.The column was pretreated with 20% triethylamine/hexanes, and then thecompound was loaded and eluted with 20 and 50% dichloromethane/hexanes.The material was further purified by recrystallization from acetonitrilefollowed by two sublimations at 250° C. to afford 1.87 g (22% yield) ofpure material.

Synthesis Compound 11

Step 1

6.8 g of pyridine was added to 9.67 g (71.5 mmol) of 2-m-tolylethanaminein 100 mL of dichloromethane. The solution was cooled to 0° C. using anice water bath. To the solution was added 10 mL of benzoyl chloride.After complete addition, the mixture was stirred at room temperature for2 hrs and quenched by water. The organic layer was separated, washedwith dilute HCl and sodium bicarbonate solution and water, dried overmagnesium sulfate, and concentrated to a residue. The product was usedfor the next step without further purification.

Step 2

17.5 g of N-(3-methylphenethyl)-2-phenylacetamide and 60 mL of POCl₃were mixed with 150 mL of xylenes. The mixture was heated to reflux for4 hrs. After cooled to room temperature, the solvent was decanted. Thesolid was dissolved with ice water. The mixture was neutralized withNaOH. The mixture was extracted with dichloromethane. The organic layerwas then washed with water and dried over magnesium sulfate. Aftersolvent evaporation, 12 g of product was obtained. The product was usedfor the next step without further purification.

Step 3

12 g of 6-methyl-l-phenyl-3,4-dihydroisoquinoline was mixed with 10 g ofPd/C (5%) in 100 mL of xylenes and heated to reflux overnight. Aftercooled to room temperature, the solid was removed by filtration. Thesolvent was then evaporated. The residue was purified by silica gelcolumn chromatography using hexanes and ethyl acetate as solvent. 7.1 gof product was obtained after final distillation.

Step 4

6.1 g (27.8 mmol) of 6-methyl-l-phenylisoquinoline and 4.3 g (12 mmol)of iridium chloride were mixed in 90 mL of 2-ethoxyethanol and 30 mL ofwater. The mixture was heated to reflux overnight. After cooled to roomtemperature, the solid was collected by filtration. 6.2 g of the dimerwas obtained. The dimer was used for the next step without furtherpurification.

Step 5

6.0 g of the dimer, 1.8 g of 2,4-pentanedione, and 2.9 g of sodiumcarbonate were added to 100 mL of 2-ethoxyethanol and heated to refluxovernight. After cooled to room temperature, the solid was collected byfiltration. The solid was then washed with dichloromethane. The filtratewas concentrated and run through a triethylamine treated silica gelcolumn. The final compound was sublimed under high vacuum. 2.0 g of99.6% pure product was obtained after sublimation.

Synthesis of Compound 12

Step 1

4-bromoisoquinoline (15 g, 72.5 mmol), methylboronic acid (8.8 g, 145mmol), K₃PO₄ (62 g, 290 mmol), Pd₂(dba)₃ (6.6 g, 7.2 mmol),2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (5.9 g, 14.4 mmol, 0.2equiv), and 350 mL of anhydrous toluene were charged to a dry 500 mLthree-neck flask. The mixture was refluxed under nitrogen for 20 hrs.After cooling, 200 mL of methylene chloride was added. The mixture wasfiltered to remove insolubles, then concentrated under vacuum. Theresulting crude material was distilled at 130° C. (first fraction at 95°C. was discarded). Approximately 9.8 g of a colorless liquid wasobtained (94% yield). The product was used for the next step withoutfurther purification (96% product, 3.5% isoquinoline).

Step 2

4-methylisoquinoline (9.5 g, 63.7 mmol) and 100 mL of dry THF werecharged to a 1 L round-bottom flask. The flask was cooled to 0° C. in anice bath, and a solution of 0.5 M 4-isopropylphenyl magnesium chloridein THF (300 mL, 150 mmol) was added dropwise. The reaction mixture wasstirred at room temperature for 4 days followed by the dropwise additionof 400 mL of water to quench the reaction. Ethyl acetate (300 mL) wasadded, and the organic layers were separated and bubbled with air for 2days with stirring. Then, the organic layer was concentrated undervacuum. The resulting oil was purified by column chromatography using10% ethyl acetate/hexanes and vacuum distilled to give 2.7 g (16% yield)of a pale yellow oil.

Step 3

1-(4-isopropylphenyl)-4-methylisoquinoline (2.7 g, 10.3 mmol, 2.2equiv), iridium chloride (1.67 g, 4.7 mmol), 40 mL of 2-ethoxyethanol,and 8 mL of water were charged to a 125 mL three-neck flask. The mixturewas heated at reflux for 24 hrs. The cooled mixture was filtered andwashed with 2-ethoxyethanol, methanol, and hexanes to afford 2.9 g of areddish-brown powder (83% yield).

Step 4

The dimer (2.9 g, 1.94 mmol), 2,4-pentanedione (1.94 g, 19.4 mmol),sodium carbonate (2.05 g, 19.3 mmol), and 30 mL of 2-ethoxyethanol werecharged to a 125 mL three-neck flask. The mixture was stirred at refluxfor 5 hrs. The cooled solution was filtered and washed with2-ethoxyethanol, methanol, and hexanes to afford 1.85 g of a red solid(97% pure), which was further purified by sublimation.

Synthesis of Compound 13

Step 1

To a 500 mL round bottle flask, 12.05 g (72.9 mmol) of2-chloroquinoline, 13.2 g (83.86 mmol) of 3,4-dimethylphenylboronicacid, 2.5 g (2.18 mmol) of Pd(PPh₃)₄, 30.0 g (214 mmol) of K₂CO₃, 150 mLof DME, and 150 mL of water were charged. The reaction mixture washeated to reflux under nitrogen overnight. The reaction mixture wascooled. The organic extracts were purified by silica gel columnchromatography (10% ethyl acetate in hexane as eluent). The materialobtained was further purified by vacuum distillation (Kugelrohr) at 200°C. to yield 15.5 g (95% yield) of product as a colorless liquid.

Step 2

8.1 g (34.7 mmol) of ligand from Step 1, 120 mL of 2-methoxyethanol, and40 mL of water were charged in a 500 mL three-neck flask. The reactionmixture was bubbled with nitrogen for 45 min with stirring. Then, 5.3 g(14.5 mmol) of IrCl₃.xH₂O was added into this mixture and heated toreflux under nitrogen for 17 hrs. The reaction mixture was cooled andfiltered. The solid was washed with methanol (3×100 mL) followed byhexane (3×100 mL). 7.8 g of the dimer (65%) was obtained after drying ina vacuum oven. The dimer was used for next step without furtherpurification.

Step 3

6.0 g of the dimer (4.3 mmol), 4.4 g of 2,4-pentanedione (43 mmol), 4.7g (43.0 mmol) of sodium carbonate, and 200 mL of 2-methoxyethanol wereadded in a 500 mL round bottle flask. The reaction mixture wasvigorously stirred at room temperature for 28 hrs. The reaction mixturewas then suction filtered and washed with methanol (3×100 mL) followedby hexane (2×100 mL). The solid was collected and stirred in ˜500 mL ofa solvent mixture (450 mL of methylene chloride and 50 mL oftriethylamine) for ˜10 min. Then the mixture was separated by silica gelcolumn (column pretreated with triethylamine/hexane) with 50% methylenechloride in hexane as elute. ˜6 g red solid was obtained as the product.

Synthesis of Compound 14

Step 1

Lithium aluminum hydride (2.65 g, 69.8 mmol) was added to 80 mL of THFthat was cooled in an ice bath. A solution of 2-amino-6-fluorobenzoicacid (10 g, 64.46 mmol) in 50 mL THF was added dropwise via a droppingfunnel. The reaction was allowed to stir overnight at room temperature.Another portion of 20 mL of 1M lithium aluminum hydride in THF wasadded, and the reaction was heated to 40° C. Upon cooling in an icebath, 3 mL of water was added carefully via a dropping funnel followedby 50 mL of 1N NaOH, and the mixture was stirred for 15 min. Next, 50 mLof water was added, and the mixture was stirred for 10 min. More NaOHsolution was added, and the emulsion was stirred overnight. The organiclayers were extracted, washed with water, and concentrated, and theresidue was dissolved in 100 mL of ethyl acetate. Hexanes were added,and a solid precipitated out and was filtered to yield 3.66 g of a tansolid, which was used for the next step.

Step 2

A mixture of (2-amino-6-fluorophenyl)methanol (3.66 g, 25.94 mmol),3′-methylacetophenone (5.6 mL, 41.50 mmol), RuCl₂(PPh₃)₃ (25 mg, 0.026mmol), and powdered potassium hydroxide (247 mg, 4.41 mmol) in 60 mL oftoluene was refluxed overnight under nitrogen in a 200 mL round-bottomflask equipped with a Dean-Stark trap under nitrogen. Upon cooling,Celite was added, and the mixture was filtered through a silica gel plugthat was eluted with ethyl acetate. The solution was evaporated to abrown oil, which was purified by column chromatography eluting with 0and 2% ethyl acetate/hexanes. The cleanest fractions were furtherpurified by Kugelrohr distillation at 220° C. to yield 4.6 g of product.

Step 3

A mixture of 5-fluoro-2-m-tolylquinoline (3.0 g, 12.64 mmol), iridiumchloride (2.13 g, 5.75 mmol), 25 mL of 2-ethoxyethanol, and 8 mL ofwater was purged with nitrogen for 20 min and then heated to refluxovernight under nitrogen. The cooled mixture was filtered, washed withwater and methanol, and allowed to air dry.

Step 4

The dimer was mixed with 2,4-pentanedione (3.0 mL, 28.8 mmol), K₂CO₃(1.23 g, 8.90 mmol), and 2-ethoxyethanol (50 mL) and heated to nearreflux under nitrogen overnight. The cooled mixture was filtered, andthe red solid rinsed with isopropanol. The solid was dissolved indichloromethane and purified on a silica gel plug. The plug was treatedwith 10% triethylamine/hexanes followed by hexanes prior to loading thematerial, and the product was eluted with dichloromethane. The fractionswith product were collected and concentrated to a small volume.Isopropanol was added, and the mixture was concentrated. Theprecipitated solid was filtered and purified by two sublimations toyield 0.82 g of product.

Synthesis of Compound 15

Step 1

A solution of 2-amino-6-methylbenzoic acid (10 g, 66.15 mmol) in 60 mLof THF was cooled in an ice-salt bath. A solution of lithium aluminumhydride in THF was added using a dropping funnel under nitrogen (2.4 M,33 mL, 79.38 mmol). The reaction was allowed to proceed overnight. Thereaction was quenched with water, then 50 mL of 1N NaOH solution wasadded dropwise as the reaction was cooled in an ice-salt bath. Next, 50mL of water was added and stirred for 1 hr, followed by 50% NaOHsolution. The mixture was extracted with dichloromethane. The organicextracts were dried over magnesium sulfate, filtered, and evaporated toa residue. The residue was purified by column chromatography elutingwith 10 to 60% ethyl acetate/hexanes to yield 7.7 g (85% yield) of a tansolid.

Step 2

A mixture of (2-amino-6-methylphenyl)methanol (7.7 g, 56.13 mmol),3′,5′-dimethylacetophenone (12.5 g, 84.20 mmol),dichlorotris(triphenylphosphine)ruthenium (III) (54 mg, 0.056 mmol), andpowdered potassium hydroxide (535 mg, 9.54 mmol) in 150 mL of toluenewas refluxed overnight under nitrogen in a 500 mL round-bottom flaskequipped with a Dean-Stark trap under nitrogen. Upon cooling, Celite wasadded, and the mixture was filtered through a silica gel plug that waseluted with ethyl acetate. The solution was evaporated to a dark oil,which was purified by column chromatography eluting with 0 to 2% ethylacetate/hexanes. A yellow oil was obtained, which solidified upon dryingon high vacuum. The solid was recrystallized from hexanes to yield 7.8 g(56% yield) of a yellow solid.

Step 3

A mixture of 5-methyl-2-(3,5-dimethylphenyl)quinoline (7.8 g, 31.54mmol), iridium chloride (3.89 g, 10.51 mmol), 45 mL of 2-ethoxyethanol,and 15 mL of water was purged with nitrogen for 20 min, then heated toreflux under nitrogen for 24 hrs. The cooled mixture was filtered,washed with water and methanol, and allowed to air dry.

Step 4

The dimer was mixed with 2,4-pentanedione (5.5 mL, 53 mmol), K₂CO₃ (1.23g, 8.90 mmol), and 2-ethoxyethanol (100 mL) and heated to 110° C. undernitrogen for 1 day. The cooled mixture was filtered, and the red solidwas rinsed with isopropanol. The solid was dissolved in dichloromethaneand purified on a silica gel plug. The plug was treated with 10%triethylamine/hexanes followed by hexanes prior to loading the material,and the product was eluted with dichloromethane. The fractions withproduct were collected and concentrated to a small volume. Isopropanolwas added, and the mixture was concentrated. The precipitated solid wasfiltered and purified by two sublimations to yield 3.73 g of product.

Synthesis of Compound 16

Step 1

2-xylyl-7-chloroquinoline (3.0 g, 11 mmol) from Step 2 of Compound 9 andiron(III) acetylacetonate (0.2 g, 0.56 mmol) were dissolved in 66 mL ofa solution of THF/1-methyl-2-pyrrolidinone (60/6) in a 250 mLround-bottom flask. Nitrogen was bubbled through the reaction mixturefor 10 min. The solution was cooled using an ice bath. 11.2 mL of 2.0 Mpropylmagnesium chloride in ether was added dropwise. The reaction wasstirred for 2 hrs, then quenched slowly with water. The reaction mixturewas allowed to warm to room temperature, and ethyl acetate was added.The organic phase was washed with water and dried over magnesiumsulfate. The solvent was removed under vacuo, and the product waschromatographed using a silica gel column with 2% ethyl acetate inhexanes as the eluent to give 2 g (67% yield) of product.

Step 2

2-(3,5-dimethylphenyl)-7-propylquinoline (2.5 g, 9.1 mmol) andiridium(III) chloride (1.3 g, 3.6 mmol) were dissolved in 50 mL of a 3:1mixture of 2-ethoxyethanol and water, respectively, in a 100 mLround-bottom flask. The solution was purged with nitrogen for 10 min,then refluxed under nitrogen for 16 hrs. The reaction mixture wasallowed to cool to room temperature, and the precipitate was filteredand washed with methanol. The dimer was then dried under vacuum and usedfor next step without further purification. 2.0 g of the dimer wasobtained after vacuum drying.

Step 3

The dimer (2.0 g, 1.3 mmol), 2,4-pentanedione (1.3 g, 1.0 mmol), andK₂CO₃ (2.0 g, 14.0 mmol) were added to 50 mL of 2-methoxyethanol andstirred at room temperature for 24 hrs. The precipitate was filtered andwashed with methanol. The solid was re-dissolved in dichloromethane andpassed through a plug with Celite, silica gel, and basic alumina. Thesolvent was evaporated under vacuum to give 1.0 g (50% yield) ofproduct.

Synthesis of Compound 17

Step 1

2-xylyl-7-chloroquinoline (3.0 g, 11 mmol) from Step 2 of Compound 9 andiron(III) acetylacetonate (0.2 g, 0.56 mmol) were dissolved in 66 mL ofa solution of THF/1-methyl-2-pyrrolidinone (60/6) in a 250 mLround-bottom flask. Nitrogen was bubbled through the reaction mixturefor 10 min. The solution was cooled using an ice bath. 11.2 mL of 2.0Misopropylmagnesium chloride in ether was added dropwise. The reactionwas stirred for 2 hrs and then quenched slowly with water. The reactionmixture was allowed to warm to room temperature, and ethyl acetate wasadded. The organic phase was washed with water and dried over magnesiumsulfate. The solvent was removed under vacuo, and the product waschromatographed using a silica gel column with 2% ethyl acetate inhexanes as the eluent to give 2 g (67%yield) of product.

Step 2

2-(3,5-dimethylphenyl)-7-isopropylquinoline (2.5 g, 9.1 mmol) andiridium(III) chloride (1.3 g, 3.6 mmol) were dissolved in 50 mL of a 3:1mixture of 2-ethoxyethanol and water, respectively, in a 100 mLround-bottom flask. The solution was purged with nitrogen for 10 min andthen refluxed under nitrogen for 16 hrs. The reaction mixture was thenallowed to cool to room temperature, and the precipitate was filteredand washed with methanol. The dimer was then dried under vacuum and usedfor next step without further purification. 2.0 g of the dimer wasobtained after vacuum drying.

Step 3

The dimer (2.0 g, 1.3 mmol), 2,4-pentanedione (1.3 g, 1.0 mmol), andK₂CO₃ (2.0 g, 14.0 mmol) were added to 50 mL of 2-methoxyethanol andstirred at room temperature for 24 hrs. The precipitate was filtered andwashed with methanol. The solid was re-dissolved in dichloromethane andpassed through a plug with Celite, silica gel, and basic alumina. Thesolvent was evaporated under vacuum to give 1.0 g (50% yield) ofproduct.

Synthesis of Compound 18

Step 1

2-xylyl-7-chloroquinoline (1.5 g, 5.6 mmol) from Step 2 of Compound 9,phenylboronic acid (1.4 g, 11.0 mmol), Pd(PPh₃)₄ (0.2 g, 0.168 mmol),and K₂CO₃ (2.3 g, 16.6 mmol) were mixed with 40 mL of DME and 40 mLwater in a 100 mL flask. The reaction mixture was heated to reflux undernitrogen overnight. The reaction was cooled, and the organic extractswere purified with a silica gel column with 2% ethyl acetate in hexanesas the eluent to give 1.0 g (58% yield) of product.

Step 2

A mixture of 0.9 g (2.9 mmol) of the ligand from Step 1 and iridium(III)chloride (0.47 g, 1.26 mmol) was dissolved in 50 mL of a 3:1 mixture of2-ethoxyethanol and water, respectively, in a 100 mL round-bottom flask.The solution was purged with nitrogen for 10 min and then refluxed undernitrogen for 16 hrs. The reaction mixture was then allowed to cool toroom temperature, and the precipitate was filtered and washed withmethanol. The dimer was then dried under vacuum and used for next stepwithout further purification. 0.61 g (50% yield) of the dimer wasobtained after vacuum drying.

Step 3

0.6 g the dimer, 2,4-pentanedione (0.37 g, 3.5 mmol), and K₂CO₃ (0.38 g,3.5 mmol) were added to 50 mL of 2-methoxyethanol and stirred at roomtemperature for 24 hrs. The precipitate was filtered and washed withmethanol. The solid was redissolved in dichloromethane and passedthrough a plug with Celite, silica gel, and basic alumina. The solventwas evaporated under vacuum to give ˜0.45 g (69% yield) of product.

Synthesis of Compound 19

Step 1

A mixture of 2-aminobenzyl alcohol (11.2 g, 89.2 mmol),5,7-dimethyl-l-tetralone (10.0 g, 55.7 mmol),dichlorotris(triphenylphosphine)ruthenium (III) (0.11 g, 0.111 mmol),and powdered potassium hydroxide (0.63 g, 11.2 mmol) in 200 mL oftoluene was refluxed overnight under nitrogen in a 500 mL round-bottomflask equipped with a Dean-Stark trap. Celite was added to the cooledreaction mixture and filtered through a silica gel plug that was elutedwith ethyl acetate. The solution was evaporated, and the residue waspurified by column chromatography eluting with 5 and 10% ethylacetate/hexanes. 10.7 g (76% yield) product was obtained.

Step 2

2.8 g (10.8 mmol) of the ligand from Step 1, 1.67 g (4.5 mmol) ofIrCl₃.xH₂O, 60 mL 2-methoxyethanol, and 20 mL water were mixed in a 100mL round flask. The reaction mixture was heated to reflux under nitrogenovernight. The reaction was cooled and filtered. The solid was washed bymethanol and hexane. 2.0 g of the dimer (50%) was obtained.

Step 3

2.0 g (1.3 mmol) of the dimer, 1.3 g (13 mmol) of 2,4-pentanedione, 1.4g (13 mmol) of sodium carbonate, and 50 mL of 2-methoxyethanol weremixed in a 100 mL flask. The reaction mixture was heated to reflux undernitrogen overnight. Upon cooling, the solid was filtered, washed bymethanol, then purified by silica gel column chromatography to afford1.2 g (57% yield) of product.

Synthesis of Compound 20

Step 1

A mixture of 2-chloroquinoline (32.8 g, 0.02 mol), 3-bromophenylboronicacid (40.53 g, 0.02 mol), Ph₃P (5.3 g, 10 mol %), Pd(OAc)₂ (2.3 g, 5 mol%), and K₂CO₃ (111.4 g, 0.08 mol) in 300 mL of dimethoxyethane and 300mL of H₂O was purged with nitrogen for 20 min and refluxed for 8 hrsunder nitrogen. The reaction was then allowed to cool to roomtemperature, and the organic phase was separated from the aqueous phase.The aqueous phase was washed with ethyl acetate. The organic fractionswere combined and dried over magnesium sulfate, and the solvent wasremoved under vacuum. The product was chromatographed using silica gelwith ethyl acetate and hexanes as the eluent to yield 55 g (95% yield)of a white solid.

Step 2

A mixture of 2-(3-bromophenyl)quinoline (10.0 g, 0.035 mol),isobutylboronic acid (7.2 g, 0.07 mol), Pd₂(dba)₃ (0.32 g, 1 mol %),2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.7 g, 4 mol %), andpotassium phosphate monohydrate (24 g, 0.1 mol) in 100 mL of toluene waspurged with nitrogen for 20 min and refluxed overnight under atmosphere.The reaction mixture was allowed to cool, and the solvent was removedunder vacuum. The crude product was chromatographed using a silica gelcolumn with 2% ethyl acetate in hexanes as the eluent. The solvent wasthen removed under vacuo to give 8.0 g of product.

Step 3

2-(3-isobutylphenyl)quinoline (5.4 g, 20.7 mmol) and iridium(III)chloride (2.5 g, 7 mmol) were dissolved in 50 mL of a 3:1 mixture of2-ethoxyethanol and water, respectively, in a 100 mL round-bottom flask.Nitrogen was bubbled through the solution for 10 min, and then themixture was refluxed under nitrogen for 16 hrs. The reaction mixture wasthen allowed to cool to room temperature, and the precipitate wasfiltered and washed with methanol. The dimer was then dried under vacuumand used for next step without further purification. 4.0 g of the dimerwas obtained after vacuum drying.

Step 4

The dimer (3.0 g, 1.8 mmol), 2,4-pentanedione (1.8 g, 18.0 mol), andK₂CO₃ (3.0 g, 18.0 mmol) were added to 100 mL of 2-methoxyethanol andstirred at room temperature for 24 hrs. The precipitate was filtered andwashed with methanol. The solid was redissolved in dichloromethane andpassed through a plug with Celite, silica gel, and basic alumina. Thesolvent was evaporated under vacuum to give 2.0 g of product.

Synthesis of Compound 21

Step 1

2-(3-bromophenyl)quinoline (10.0 g, 35 mmol) from Step 1 of Compound 20,1,2-bis(diphenylphosphino)ethane]dichloronickel(II) (0.5 g, 0.9 mmol),and 100 mL anhydrous THF were mixed in a 500 mL round-bottom flask.Nitrogen was bubbled through the mixture, and the flask was placed in anice bath for 30 min. 88 mL of 2.0 M propylmagnesium bromide in ether wasadded dropwise to the reaction mixture over a period of 20 min afterwhich the mixture was further stirred for 30 min and then quenched withwater. The mixture was brought to room temperature, and ethyl acetatewas added. The water layer was removed. The organic phase was dried overmagnesium sulfate, and the solvent was removed in vacuo. The product waschromatographed using a silica gel column with ethylacetate and hexanesas the eluent. The solvent was once again removed to give 5 g ofproduct.

Step 2

2-(3propylphenyl)quinoline (3.2 g, 13.0 mmol) and iridium(III) chloride(1.8 g, 5.2 mmol) were dissolved in 50 mL of a 3:1 mixture of2-ethoxyethanol and water, respectively, in a 100 mL round-bottom flask.Nitrogen was bubbled through the solution for 10 min and then refluxedunder nitrogen for 16 hrs. The reaction mixture was then allowed to coolto room temperature, and the precipitate was filtered and washed withmethanol. The dimer was then dried under vacuum and used for next stepwithout further purification. 2.6 g of the dimer was obtained aftervacuum drying.

Step 3

The dimer (2.6 g, 1.8 mmol), 2,4-pentanedione (1.8 g, 18.0 mol), andK₂CO₃ (3.0 g, 18.0 mmol) were added to 100 mL of 2-methoxyethanol andstirred at room temperature for 24 hrs. The precipitate was filtered andwashed with methanol. The solid was redissolved in dichloromethane andpassed through a plug with Celite, silica gel, and basic alumina. Thesolvent was evaporated under vacuum to give 2.0 g of product.

Synthesis of Compound 22

Step 1

4.8 g (29 mmol) of 1-chloroisoquinoline, 5.3 g (35 mmol) of3,5-dimethylphenylboronic acid, 20 g (87 mmol) of potassium phosphate,0.5 g (1.16 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl,100 mL of toluene, and 30 mL of water were mixed in a three-neck flask.The system was bubbled with nitrogen for 30 min. 0.27 g (0.29 mmol) ofPd₂(dba)₃ was added, and the mixture was heated to reflux for 4 hrs.After cooled to room temperature, the reaction mixture was filteredthrough a Celite bed. The product was columned with 2% ethyl acetate andhexanes. 6.0 g (87% yield) of product was obtained after column.

Step 2

5.5 g (23.6 mmol) of 1-(3,5-dimethylphenyl)isoquinoline, and 3.4 g (9.5mmol) of iridium chloride were mixed in 90 mL of 2-ethoxyethanol and 30mL of water. The mixture was purged with nitrogen for 10 min and thenheated to reflux for 24 hrs. After cooled to room temperature, the solidwas collected by filtration. The solid was thoroughly washed withmethanol and hexanes. The product was dried under vacuum. 4.6 g (70%yield) of solid was obtained and used for the next step without furtherpurification.

Step 3

4.5 g (3.25 mmol) of the dimer, 3.3 g (32.5 mmol) of 2,4-pentanedione,and 1.7 g (16.3 mmol) of sodium carbonate were refluxed in 150 mL of2-ethoxyethanol for 10 hrs. After cooled to room temperature, themixture was filtered through a Celite bed and washed thoroughly withmethanol. The red solid on top was then washed with dichloromethane. Theproduct was purified by column chromatography using 1:1 dichloromethaneand hexanes as eluent. 1.6 g of product was obtained. The product wasfurther purified by high vacuum sublimation at 220° C.

Synthesis of Compound 23

Step 1

Dichloroiodobenzene (37.0 g 136 mmol), Pd₂(dba)₃ (1.5 g, 1.6 mmol), andlithium chloride (29.0 g, 682 mmol) were dissolved in 100 mL of DMF in a500 mL round-bottom flask. 64.0 mL of acetic anhydride and 47.0 mL ofN-ethyldiispropylamine were then added to the reaction mixture. Thereaction was heated to 100° C. for 8 hrs. Water was added to thereaction mixture, and the product was extracted with ethyl acetate andchromatographed using a silica gel column with ethyl acetate and hexanesas the eluent. 8 g of product was obtained.

Step 2

2-aminobenzyl alcohol (6.0 g, 48 mmol), 3,5-dichloroacetophenone (12.0g, 63.5 mmol), RuCl₂(PPh₃)₃ (0.5 g, 10 mol %), and potassium hydroxide(2.4 g, 42.0 mmol) was refluxed in 100 mL of toluene for 10 hrs. Waterwas collected from the reaction using a Dean-Stark trap. The reactionmixture was allowed to cool to room temperature and filtered through asilica gel plug. The product was further purified with a silica gelcolumn using 2% ethyl acetate in hexanes as the eluent. 4.0 g (30%yield) product was obtained after column. The product was furtherrecrystallized from isopropanol. 3.5 g of product was obtained.

Step 3

2-(3,5-dichlorophenyl)quinoline (4.0 g, 14.6 mmol), isobutylboronic acid(6.0 g, 58.4 mol), Pd₂(dba)₃ (0.13 g, 1 mol %),2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.24 g, 4 mol %), andpotassium phosphate monohydrate (10 g, 13.8 mmol) were mixed in 100 mLof toluene in a 250 mL round-bottom flask. Nitrogen was bubbled throughthe mixture for 20 min, and the mixture was refluxed under nitrogenovernight. The reaction mixture was allowed to cool, and the solventremoved under vacuum. The crude product was chromatographed using asilica gel column with 2% ethyl acetate in hexanes as the eluent. Thesolvent was then removed under vacuo to give 3.5 g of product.

Step 4

2-(3,5-diisobutylphenyl)quinoline (3.0 g, 9.50 mmol) and iridium(III)chloride (0.70 g, 2.4 mmol) were dissolved in 50 mL of a 3:1 mixture of2-ethoxyethanol and water, respectively, in a 100 mL round-bottom flask.Nitrogen was bubbled through the solution for 10 min and then refluxedunder a nitrogen for 16 hrs. The reaction mixture was then allowed tocool to room temperature, and the precipitate was filtered and washedwith methanol. The dimer was then dried under vacuum and used for nextstep without further purification. 2.0 g of the dimer was obtained aftervacuum drying.

Step 5

A mixture of the dimer, 2,4-pentanedione, and K₂CO₃ in 2-methoxyethanolis stirred at room temperature for 24 hrs. The precipitate is filteredand washed with methanol. The solid is redissolved in dichloromethaneand passed through a plug with Celite, silica gel, and basic alumina.The solvent is evaporated under vacuum to give the product.

Synthesis of Compound 24

Step 1

10.6 g (78.4 mmol) of 2-p-tolylethanamine, 10.7 g (71.2 mmol) of3,5-dimethylbenzoic acid, and 0.5 g of boric acid were heated to refluxin 200 mL of p-xylene with a Dean-Stark trap overnight. After cooled toroom temperature, 400 mL of hexanes was added. The solid was collectedby filtration. The product was dried under vacuum. 16.9 g of white solidwas obtained. The product was used for the next step without furtherpurification.

Step 2

6.9 of 3,5-dimethyl-N-(4-methylphenethyl)benzamide, 60 mL of POCl₃, and50 g of P₂O₅ were refluxed in 150 mL of p-xylene under nitrogen for 4hrs. After cooled to room temperature, the solvent was decanted. Thesolid was dissolved with ice cold water. The solution was neutralizedwith potassium hydroxide solution, then extracted with toluene. Aftersolvent evaporation, the residue was purified by column chromatographyusing 1:3 hexanes and ethyl acetate. 12 g (76%) of product was obtained.

12 g (48 mmol) of1-(3,5-dimethylphenyl)-7-methyl-3,4-dihydroisoquinoline and 2.0 g of 10%palladium on carbon were refluxed in 200 mL of p-xylene for 4 hrs. Aftercooled to room temperature, the reaction mixture was filtered through aCelite bed. The product was then purified by column using 5% ethylacetate in hexanes as eluent. 10 g of product was obtained. The productwas further purified by recrystallizing from hexanes three times. 6.2 gof pure product was obtained after multiple recrystallizations.

5.5 g (22 mmol) of 1-(3,5-dimethylphenyl)isoquinoline and 2.64 g (7.4mmol) of iridium chloride were mixed in 90 mL of 2-ethoxyethanol and 30mL of water. The mixture was purged with nitrogen for 10 min and thenheated to reflux for 14 hrs. After cooled to room temperature, the solidwas collected by filtration. The solid was thoroughly washed withmethanol and hexanes. The product was dried under vacuum. 3.75 g (70%yield) of the dimer was obtained, which was used for next step withoutfurther purification.

Step 3

3.7 g (2.6 mmol) of the dimer, 2.6 g (26 mmol) of 2,4-pentanedione, and1.4 g (13 mmol) of sodium carbonate were reacted in 150 mL of2-ethoxyethanol at room temperature for 72 hrs. Deep red precipitateformed. The mixture was filtered through a Celite bed and washedthoroughly with methanol. The red solid on top was then washed withdichloromethane. 3.6 g of product was obtained. The product was furtherpurified by high vacuum sublimation at 235° C.

Exemplary and Comparative Devices

All devices are fabricated by high vacuum (<10⁻⁷ Ton) thermalevaporation. The anode electrode is ˜1200 Å of indium tin oxide (ITO).The cathode consists of 10 Å of LiF followed by 1,000 Å of A1. Alldevices are encapsulated with a glass lid sealed with an epoxy resin ina nitrogen glove box (<1 ppm of H₂O and O₂) immediately afterfabrication, and a moisture getter was incorporated inside the package.

The organic stack consists of sequentially, from the ITO surface, 100 Åthick of Ir(3-Meppy)₃ as the hole injection layer (HIL), 400 Å of4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD) as the holetransporting layer (HTL), 300 Å of BAlq doped with 6-12 wt % of thedopant emitter (exemplary compounds and comparative compounds) as theemissive layer (EML), 550 Å of tris(8-hydroxyquinolinato)aluminum (Alq₃)as the electron transport layer (ETL). The current-voltage-luminance(IVL) characteristics and operational lifetimes are measured andsummarized in the Table 1. The device performance is compared at 10mA/cm² and lifetime is compared at J=40 mA/cm² (constant dc) at roomtemperature and 70° C.

Additional Devices with Compound 1

Using the general method as described above and the additional materialsdescribed below, the following devices were fabricated using compound 1as the dopant emitter:

Devices with Compound 1

Device Device description 1a ITO/Compound A (100 Å)/NPD (400 Å)/BAlq:Compound 1 (6%) (300 Å)/Alq3 (550 Å)/LiF/Al 1b ITO/Compound A (100Å)/NPD (400 Å)/BAlq: Compound 1 (9%) (300 Å)/Alq3 (550 Å)/LiF/Al 1cITO/Compound A (100 Å)/NPD (400 Å)/BAlq: Compound 1 (12%) (300 Å)/Alq3(550 Å)/LiF/Al 1d ITO/Compound A (100 Å)/NPD (400 Å)/BAlq: Compound A(10%): Compound 1 (3%) (300 Å)/Balq (100)/Alq3 (450 Å)/LiF/Al 1eITO/Compound A (100 Å)/NPD (400 Å)/Compound B: Compound 1 (12%) (300Å)/Alq3 (550 A)/LiF/Al 1f ITO/Compound A (100 Å)/NPD (400 Å)/Compound B:Compound 1 (12%) (300 Å)/Compound B (100 Å )/ Alq3 (450 Å)/LiF/Al 1gITO/Compound A (100 Å)/NPD (400 Å)/Compound C: Compound 1 (6%) (300Å)/Alq3 (550 Å)/LiF/Al 1h ITO/Compound A (100 Å)/NPD (400 Å)/Compound C:Compound 1 (9%) (300 Å)/Alq3 (550 Å)/LiF/Al 1i ITO/Compound A (100Å)/NPD (400 Å)/Compound C: Compound 1 (12%) (300 Å)/Alq3 (550 Å)/LiF/AlPerformance of Devices with Compound 1

At 500 nits T_(80%) at 40 mA/cm² (hr) Device EML dopant % λ max CIE V(V) LE (cd/A) EQE (%) L₀ (cd/m²) RT 70° C. 1a 6 620 0.66 7.7 21.9 19.006472 n.m. 62 0.33 1b 9 622 0.67 7.1 20.2 19.17 6447 n.m. 62 0.33 1c 12622 0.67 6.9 18.7 18.00 6382 n.m. 73 0.33 1d 3 618 0.66 7.8 27.1 22.9n.m. n.m. n.m. 0.34 1e 12 626 0.673 6.8 15.6 17 5098 n.m. n.m. 0.325 1f12 626 0.673 7.8 16.3 17.6 5041 n.m. n.m. 0.325 1g 6 622 0.668 6.1 2019.3 6137 287 31 0.330 1h 9 624 0.671 5.7 18.2 18.4 5798 470 42 0.327 1i12 625 0.672 5.4 17.6 18.2 5779 704 58 0.327Additional Devices with Compound 9

Using the general method as described above, the following devices werefabricated using compound 9 as the dopant emitter.

Devices with Compound 9

Device Device description 9a ITO/Compound A (100 Å)/NPD (400 Å)/ BAlq:Compound 9 (6%) (300 Å)/Alq3 (550 Å)/LiF/Al 9b ITO/Compound A (100Å)/NPD (400 Å)/BAlq: Compound 9 (9%) (300 Å)/Alq3 (550 Å)/LiF/Al 9cITO/Compound A (100 Å)/NPD (400 Å)/BAlq: Compound 9 (12%) (300 Å)/Alq3(550 Å)/LiF/Al 9d ITO/Compound A (100 Å)/NPD (400 Å)/BAlq: Compound A(10%): Compound 9 (3%) (300 Å)/ Balq (100)/Alq3 (450 Å)/LiF/Al 9eITO/Compound A (100 Å)/NPD (400 Å)/BAlq: Compound A (10%): Compound 9(3%) (300 Å)/ Alq3 (550 Å)/LiF/Al 9f ITO/Compound A (100 Å)/NPD (400Å)/Compound C: Compound 9 (9%) (300Å)/Compound C (100 Å)/ Alq3 (450Å)/LiF/Al 9g ITO/Compound A (100 Å)/NPD (400 Å)/Compound C: Compound 9(9%) (300 Å)/BAlq (100 Å)/Alq3 (450 Å)/LiF/Al 9h ITO/Compound A (100Å)/NPD (400 Å)/Compound C: Compound 9 (9%) (300 Å)/Alq3 (550 Å)/LiF/Al9i ITO/Compound A (100 Å)/NPD (400 Å)/ Compound C: Compound A (10%):Compound 9 (3%) (300 Å)/ Compound C (100 Å)/Alq3 (450 Å)/LiF/Al 9jITO/Compound A (100 Å)/NPD (400 Å)/Compound C: Compound A (10%):Compound 9 (3%) (300 Å)/ BAlq (100 Å)/Alq3 (450 Å)/LiF/Al 9kITO/Compound A (100 Å)/NPD (400 Å)/Compound C: Compound A (10%):Compound 9 (3%) (300 Å)/ Alq3 (550 Å)/LiF/AlPerformance of Devices with Compound 9

At 1000 nits T_(80%) at 40 mA/cm² (hr) Device EML dopant % λ max CIE V(V) LE (cd/A) EQE (%) L₀ (cd/m²) RT 70° C. 9a 6 615 0.653 8.6 25.5 19.507892 333 55 0.345 9b 9 616 0.654 8 26.5 20.80 8215 352 55 0.343 9c 12617 0.656 7.7 24.2 19.30 7992 330 60 0.342 9d 3 612 0.647 6.3 29.4 21.19809 n.m. 106 0.349 9e 3 612 0.642 6.3 14.6 10.3 6950 n.m. 102 0.352 9f9 618 0.659 5.6 25.6 21.1 7971 n.m. 34 0.339 9g 9 618 0.659 6.3 25.621.1 7871 n.m. 25 0.339 9h 9 618 0.659 5.5 24.5 20.4 7642 n.m. 33 0.3389i 3 612 0.646 4.8 34.6 24.5 11334 n.m. 45 0.351 9j 3 612 0.646 5.4 3323.5 10775 n.m. 41 0.351 9k 3 612 0.646 5 25.2 18 9131 n.m. 38 0.351Additional Devices with Compound 22

Using the general method as described above, the following devices werefabricated using compound 22 as the dopant emitter.

Devices with Compound 22

Device Device description 22a ITO/Compound A (100 Å)/NPD (400 Å)/BAlq:Compound 22 (6%) (300 Å)/Alq3 (550 Å)/LiF/Al 22b ITO/Compound A (100Å)/NPD (400 Å)/BAlq: Compound 22 (9%) (300 Å)/Alq3 (550 Å)/LiF/Al 22cITO/Compound A (100 Å)/NPD (400 Å)/BAlq: Compound 22 (12%) (300 Å)/Alq3(550 Å)/LiF/Al 22d ITO/Compound A (100 Å)/NPD (400 Å)/BAlq: Compound A(10%): Compound 22 (3%) (300 Å)/Balq (100)/Alq3 (450 Å)/LiF/AlPerformance of Devices with Compound 22

At 1000 nits T_(80%) at 40 mA/cm² (hr) Device EML dopant % λ max CIE V(V) LE (cd/A) EQE (%) L₀ (cd/m²) RT 70° C. 22a 6 635 0.693 10 10.8 18.33,500 n.m. 62 0.304 22b 9 637 0.695 9.9 10.5 18.5 3,408 n.m. 73 0.30322c 12 637 0.693 9.5 10 17.7 3,277 n.m. 80 0.304 22d 3 633 0.691 9.413.6 21.1 3,445 n.m. 116 0.307

1-22. (canceled)
 23. A compound, which is selected from the groupconsisting of:


24. The compound of claim 23, which is:


25. The compound of claim 23, which is:


26. The compound of claim 23, which is:


27. The compound of claim 23, which is:


28. The compound of claim 23, which is:


29. The compound of claim 23, which is:


30. An organic light emitting device comprising: an anode; a cathode;and an emissive organic layer, disposed between the anode and thecathode, the organic layer comprising a compound selected from the groupconsisting of:


31. The device of claim 30, wherein the organic emissive layer furthercomprises BAlq or


32. The device of claim 30, wherein the compound is:


33. The device of claim 32, wherein the organic emissive layer furthercomprises BAlq or


34. The device of claim 30, wherein the compound is:


35. The device of claim 34, wherein the organic emissive layer furthercomprises BAlq or


36. The device of claim 30, wherein the compound is:


37. The device of claim 36, wherein the organic emissive layer furthercomprises BAlq or


38. The device of claim 30, wherein the compound is:


39. The device of claim 38, wherein the organic emissive layer furthercomprises BAlq or


40. The device of claim 30, wherein the compound is:


41. The device of claim 40, wherein the organic emissive layer furthercomprises BAlq or


42. The device of claim 30, wherein the compound is:


43. The device of claim 42, wherein the organic emissive layer furthercomprises BAlq or